Direct heteroarylation polymerization was employed to synthesize a novel low bandgap polymer, used as a p-type material of polymer photovoltaic cells. To achieve low bandgap of conjugated polymers, electron donor-acceptor (D-A) alternating strategy was used. The electron-donating 3-alkylthiophene and electron-withdrawing cyanothiophene were coupled to be polymerized via direct heteroarylation polymerization. The cyano moiety of the polymer backbone allowed a strong intermolecular interaction between neighboring chains and improved the structural perfection of the crystal structure on the substrate. The solar cell devices of ITO/PEDOT:PSS/P3HT:PCBM/LiF/Al were fabricated on ITO-coated glass substrate.